EP1224151A1 - A high pressure and high temperature reaction system - Google Patents

A high pressure and high temperature reaction system

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Publication number
EP1224151A1
EP1224151A1 EP00959090A EP00959090A EP1224151A1 EP 1224151 A1 EP1224151 A1 EP 1224151A1 EP 00959090 A EP00959090 A EP 00959090A EP 00959090 A EP00959090 A EP 00959090A EP 1224151 A1 EP1224151 A1 EP 1224151A1
Authority
EP
European Patent Office
Prior art keywords
conduit
fluid
temperature
reaction system
corrosive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00959090A
Other languages
German (de)
French (fr)
Other versions
EP1224151B1 (en
Inventor
Anders Gidner
Lars Stenmark
Stefan Elfors
Jan Abrahamsson
Kim Carlsson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HOLLINGFORD Ltd
Original Assignee
Chematur Engineering AB
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Filing date
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Publication of EP1224151A1 publication Critical patent/EP1224151A1/en
Application granted granted Critical
Publication of EP1224151B1 publication Critical patent/EP1224151B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/433—Mixing tubes wherein the shape of the tube influences the mixing, e.g. mixing tubes with varying cross-section or provided with inwardly extending profiles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/30—Injector mixers
    • B01F25/31—Injector mixers in conduits or tubes through which the main component flows
    • B01F25/313—Injector mixers in conduits or tubes through which the main component flows wherein additional components are introduced in the centre of the conduit
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
    • B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F35/91—Heating or cooling systems using gas or liquid injected into the material, e.g. using liquefied carbon dioxide or steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/02—Feed or outlet devices therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/06—Treatment of sludge; Devices therefor by oxidation
    • C02F11/08—Wet air oxidation
    • C02F11/086—Wet air oxidation in the supercritical state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B01J2219/00063—Temperature measurement of the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00245—Avoiding undesirable reactions or side-effects
    • B01J2219/00247—Fouling of the reactor or the process equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0218—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of ceramic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0236—Metal based
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0277—Metal based
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention generally relates to an apparatus for mitigation of corrosion in a high pressure and high temperature reaction system, specifically in a system suitable for oxidative waste treatment under supercritical water conditions.
  • the invention relates further to the reaction system itself and to a method in said reaction system.
  • SCWO supercritical water oxidation
  • Supercritical water oxidation is a novel and advanced process for, inter alia, effective destruction of toxic substances, particularly organic pollutions, in wastewater and sludge.
  • the process converts, fast and effectively, organic materials containing substantially carbon and hydrogen to carbon dioxide and water, at a temperature above the critical point of water
  • Heavy metals present during the process are converted to their oxides whereas sulfur and phosphorous are converted to sulfate and phosphate, respectively.
  • Halogens are converted to their corresponding acids, e.g., hydrochloric acid.
  • Smaller amounts of nitrogen compounds, e.g. amines and ammonia, which exist in the waste material flow, are converted to molecular nitrogen, and not to NO ⁇ , which is an acidifying and fertilizing residual product and therefore undesirable in the effluent.
  • the waste material contains large amounts of ammonia and/or organic nitrogen compounds, substantial amounts of the nitrogen source may be found in the effluent as ammonia as a result of the destruction process. This phenomenon is undesirable as ammonia constitutes a fertilizing compound. Besides, discharge of ammonia without further purifying is very often imposed with restrictions.
  • the nitric acid has to be dosed with high accuracy relative to the amount of ammonia (a stoichiometric amount is needed) . If too little nitric acid is supplied, a remaining amount of ammonia will be left whereas too large amounts of nitric acid will result in an excess of nitrate in the effluent.
  • nickel-based alloys such as Hastelloy or Inconel
  • Acids and not at least nitric acid, are, however, in presence of oxygen strongly corrosive at high temperatures, though still subcritical ones, even if these corrosion resistant nickel alloys are used, see, e.g. The Corrosion of Nickel-base Alloy 625 in Sub- and Supercri tical Agueous Solutions of HN0 3 in the Presence of Oxygen, P. Kritzer et al., J. Mater. Sci. Lett., 1999, in print, and references therein.
  • the chlorine element As regards corrosion, generally the most troublesome compound in the supercritical water oxidation process is the chlorine element, since it is very common in various chemical substances. If the chlorine is present as an ion at elevated temperatures, it will corrode the construction materials mentioned above. The chlorine may have been an ion originally, liberated during heat up or in the reactor.
  • US 5,358,645 issued to Hong et al. disclose an apparatus and process for high temperature water oxidation, the apparatus (not in detail described) having a surface area, that may be exposed to corrosive material, composed of zirconia based ceramics.
  • the ceramics may be employed as coatings or linings.
  • US 5,461,648 issued to Nauflett et al . disclose a supercritical water oxidation reactor with a corrosion-resistant lining.
  • the inner surface of the reactor vessel is coated with artificial ceramic or diamond.
  • a cylindrical baffle for introducing the oxygenating agent extends axially within the interior of the vessel and has its exterior surface inside the vessel coated with said artificial ceramic or diamond.
  • US 5,552,039 issued to McBrayer, Jr. et al. disclose a turbulent flow cold-wall reactor. It mentions, inter alia, that if the atmosphere in the reaction chamber is harsh and corrosive, the inside wall of the reaction chamber should preferably be made of or covered with a coating or a liner withstanding the harsh atmosphere .
  • a further object of the present invention is to provide a method for disposing of waste using said apparatus.
  • An advantage of the present invention is that it allows the main parts of the reaction system, including the reactor itself, to be constructed of a relatively inexpensive material such as nickel based and nickel-chromium alloys, and still use or be able to treat corrosive materials in the process.
  • Fig. 1 shows a simplified block diagram of a reaction system suitable for oxidative waste treatment under supercritical water conditions wherein the present invention may be employed.
  • Fig. 2 shows, in cross-section, a first embodiment of an apparatus according to the present invention.
  • Fig. 3 shows, in cross-section, a second embodiment of an apparatus according to the present invention.
  • a conventional reaction system 10 comprises a primary tank 12, a heat exchanger 14, a heater 16 and a reaction chamber 18.
  • a primary wastewater stream 20 passes initially through the first compartment (not shown) of the heat exchanger 14, then through the heater 16, and enters the reaction chamber 18 under pressure, after it has been mixed with oxidant coming through feed line 22.
  • the organic matter contained in the primary waste stream 20 is oxidized, and in sequence, the hot effluence passes through the second compartment (not shown) of the heat exchanger 14.
  • heat exchangers usually have two compartments, physically isolated from each other, which, however, are heat-communicating. The second compartment transfers heat to the first compartment.
  • Constructing materials for the reactor and the tubing may comprise steel, nickel-based alloys, platinum, gold, titanium, zirconium, ceramics, ceramic composites and other corrosion resistant materials as the environment inside the reaction chamber and tubing may be hostile and corrosive.
  • nickel based alloys such as Hastelloy or Inconel
  • nitric acid As already discussed in the prior art, there is a number of species that are very aggressive relative to these nickel based alloys within a finite temperature range, among them nitric acid, sulfuric acid and hydrochloric acid. All these three acids are strongly corrosive between about 270 and 380°C, but the corrosion rates for the latter two acids are lower by a factor of ten than the one found for nitric acid, see said Kritzer article.
  • the present inventors have realized that if the initial temperatures and the temperature of the cooled effluent are kept preferably well below 270°C and the temperature in the reaction chamber is kept preferably above 380°C, there is generally only two sections of a reaction system made of nickel-based alloy that may be attacked by corrosive agents such as those mentioned above contained in, or supplied to, the wastewater flow, namely a "heating” section and a “cooling” section, where the temperatures are within the temperature interval of said corrosion.
  • the present invention is thus concerned with such sections of the reaction system and how to design them in order to provide a reaction system of low cost and good corrosion resistance.
  • the idea is to provide appropriate tubing (made of nickel based alloy or other, preferably relatively inexpensive, material that is not corrosive resistant) of the system with a corrosive resistant tube or liner.
  • the number of tubes or liners, their positions and their lengths are chosen in order to protect the system from corroding.
  • corrosion-resistant material refers to unconventional expensive material which is corrosion- resistant relative a wide variety of harsh media such as acids, particularly the acids discussed above, halogens and the like, respectively. Examples of corrosion-resistant materials will be given below.
  • a first embodiment of the present invention depicts an apparatus 101 for introducing nitric acid in a supercritical water flow containing ammonia or ammonium with the purpose of converting this to molecular nitrogen.
  • a separate tube or liner 105 of a corrosion resistant material is mounted, the outer surface of which is in fit with the inner surface of reaction system tube 103.
  • tube 105 constitutes part of the reaction system tube 103 itself (not shown) .
  • a feeding pipe 107 of relatively small diameter is mounted through an opening of tube 103 and extends substantially axially with tube 103 and liner 105, and which ends in the interior of tube 103.
  • feeding pipe 107 and tube 103 are concentrically arranged for transportation of fluids, the former nitric acid and the latter preheated wastewater feed, in the same directions, as indicated by arrows 109-113.
  • the temperature of the wastewater should preferably be above 380°C, and the temperature of the nitric acid should be low, preferably considerably lower than 270°C.
  • the concentration of the corrosive agent is low, these temperature limits are not very crucial, i.e., the corrosion would be low at temperatures slightly lower than 380°C and, particularly, at temperatures slightly higher than 270°C, e.g., 300°C.
  • the length of the liner 105 should be of at least this length, and it should be localized to protect the inner walls of tube 103 within this length.
  • the liner 105 may have an offset 117 in the end facing the end of the feeding pipe, i.e. extend beyond (upstream of) said feeding pipe end to avoid any risk of corrosion in that region.
  • the material of the liner and preferably of the feeding pipe is chosen according to its corrosion resistance relative nitric acid at the occurring temperatures.
  • Literature data shows that titanium, generally, is a suitable material, but also materials such as zirconium, platinum, tantalum, niobium and ceramics may be chosen.
  • the entire liner, or an inner coating thereof, may be constructed of such material.
  • tube 103 is provided with an elbow at the downstream end of the mixing length to prevent liner 105 from moving further downstream.
  • any suitable means for positioning and/or holding the liner e.g. flanges at the inner walls of tube 103, may be used.
  • nitric acid may safely be introduced without severe corrosion of the reaction system.
  • nitric acid and ammonia and/or ammonium will take part as early as in the section of the reaction system where the liner is localized, which further reduces the risk for severe corrosion.
  • feeding pipe 107 and tube 103 of Fig. 2 may be arranged for transportation of a wastewater feed containing a corrosive agent such as a halogen, and water or a wastewater feed in lack of such a corrosive agent, respectively.
  • a corrosive agent such as a halogen
  • the water or wastewater in tube 103 is preferably at a supercritical temperature, whereas the corrosive wastewater may be cooler.
  • a separate tube or liner 205 of a corrosion resistant material is mounted in a section of a reaction system tube 203, which is preferably at the effluent output or elsewhere in the exit path tubing.
  • the outer surface of liner 205 is arranged to be in fit with the inner surface of the reaction system tube 203.
  • a first input tube 207 is mounted through an opening of tube 203 and extends substantially axially, preferably concentrically, with tube 203 and liner 205, and which ends in the interior of tube 203.
  • a second input tube 208 is connected to tube 203 upstream from said end of input tube 207.
  • Input tube 207 and input tube 208 are arranged for transporting effluent from reactor 18 containing corrosive compounds such as nitric acid, sulfur acid, or the like, and quench water, respectively, in the directions as indicated by arrows 209-213.
  • the effluent stream is supercritical or close to supercritical, and the temperature of the quench water is low, preferably at ambient temperature.
  • the effluent input through tube 207 will be cooled effectively by the quench water and get mixed with it.
  • the flow rates are such that the total flow (effluent and quench water) will have a temperature of below a certain temperature, e.g. 270°C, depending on concentration of corrosive compounds, after having reached a steady temperature state a certain distance 215 from the end of the input tube 207, said distance being referred to as the mixing length.
  • the length of the liner 205 should be at least of this mixing length, and it should be localized to protect the inner walls of tube 203 within this length.
  • the liner 203 may have an offset 217 in the end facing the end of tube 207, i.e. extend beyond (upstream of) said tube end, to avoid any risk of corrosion in that region.
  • the material of the liner and preferably of tube 207, as well as suitable means for positioning and/or holding the liner in place may be chosen as in the first embodiment.
  • the first and the second embodiments of the present invention may be modified to include a heat exchange for assisting in increasing or decreasing the temperature in tubes 103 and 203, respectively.
  • the lengths of liners 105 and 205, respectively may be shortened.
  • an effluent from the reactor containing chlorine ions is pre-cooled in a heat exchanger by part of the incoming waste stream, to a temperature well above 380°C, e.g., 400°C.
  • the effluent is then cooled by an apparatus according to the present invention to a sufficient low temperature, e.g., 260°C, to minimize corrosion.
  • the effluent water mixture is further cooled by the remaining of the waste stream.

Abstract

In a high pressure and high temperature reaction system suitable for oxidative waste treatment, particularly a reaction system for supercritical water oxidation (SCWO), a method is disclosed for injecting a first fluid of a first temperature at a first flow rate into a second fluid of a second temperature at a second flow rate, mixing the first and the second fluids within a mixing length ( 115, 215 ), and wherein the first and second temperatures and the first and second flow rates are selected such that a temperature of the mixed fluids downstream of said mixing length ( 115, 215 ) is obtained, at which said first fluid being substantially non-corrosive.

Description

A HIGH PRESSURE AND HIGH TEMPERATURE REACTION SYSTEM
TECHNICAL FIELD OF THE INVENTION
The present invention generally relates to an apparatus for mitigation of corrosion in a high pressure and high temperature reaction system, specifically in a system suitable for oxidative waste treatment under supercritical water conditions. The invention relates further to the reaction system itself and to a method in said reaction system.
DESCRIPTION OF RELATED ART AND BACKGROUND OF THE INVENTION
Several approaches for disposing of waste are available today, of which the major ones are landfilling and incineration. In recent years, another technique based on supercritical water oxidation (SCWO) has been commercialized, see, e.g. Supercritical Water Oxidation Aims for Wastewater Cleanup, CM. Caruana, Chem. Eng. Prog., April 1995.
Supercritical water oxidation is a novel and advanced process for, inter alia, effective destruction of toxic substances, particularly organic pollutions, in wastewater and sludge. The process converts, fast and effectively, organic materials containing substantially carbon and hydrogen to carbon dioxide and water, at a temperature above the critical point of water
(374°C and 22,13 MPa), while releasing energy. The process may be completely contained and the destruction efficiency is often higher than 99%.
Heavy metals present during the process are converted to their oxides whereas sulfur and phosphorous are converted to sulfate and phosphate, respectively. Halogens are converted to their corresponding acids, e.g., hydrochloric acid. Smaller amounts of nitrogen compounds, e.g. amines and ammonia, which exist in the waste material flow, are converted to molecular nitrogen, and not to NOχ, which is an acidifying and fertilizing residual product and therefore undesirable in the effluent.
If, however, the waste material contains large amounts of ammonia and/or organic nitrogen compounds, substantial amounts of the nitrogen source may be found in the effluent as ammonia as a result of the destruction process. This phenomenon is undesirable as ammonia constitutes a fertilizing compound. Besides, discharge of ammonia without further purifying is very often imposed with restrictions.
It is known in the literature, e.g. through Reactions of Ni tra te Sal ts wi th Ammonia in Supercri tical Wa ter, P.C. Dell 'Oreo et al., Ind. Eng. Chem. , Vol. 36, No. 7, 1997, and references therein, that ammonia can be converted to molecular nitrogen during supercritical water oxidation conditions if nitric acid is used as a co-oxidant together with molecular oxygen, hydrogen peroxide or another suitable compound. The nitric acid has preferably to be supplied to the waste material flow firstly after that the organic contents have been destructed with oxygen as nitrate otherwise will compete with oxygen in the destruction of the organic contents. Furthermore, the nitric acid has to be dosed with high accuracy relative to the amount of ammonia (a stoichiometric amount is needed) . If too little nitric acid is supplied, a remaining amount of ammonia will be left whereas too large amounts of nitric acid will result in an excess of nitrate in the effluent.
For purposes of strength and corrosion, nickel-based alloys, such as Hastelloy or Inconel, are employed for manufacturing of equipment for SCWO. Acids, and not at least nitric acid, are, however, in presence of oxygen strongly corrosive at high temperatures, though still subcritical ones, even if these corrosion resistant nickel alloys are used, see, e.g. The Corrosion of Nickel-base Alloy 625 in Sub- and Supercri tical Agueous Solutions of HN03 in the Presence of Oxygen, P. Kritzer et al., J. Mater. Sci. Lett., 1999, in print, and references therein. It was found in the temperature-resolved corrosion measurements reported that the corrosion due to nitric acid was most severe at temperatures between about 270°C and 380°C, the same temperature range in which general corrosion is caused by the mixtures HCl/02 and H2S04/02, respectively. At supercritical temperatures the corrosion rates were low.
For this reason, particular solutions must be employed for the entry of nitric acid into the supercritical wastewater flow containing ammonia or ammonium salts to avoid or at least minimize the corrosion.
However, as regards corrosion, generally the most troublesome compound in the supercritical water oxidation process is the chlorine element, since it is very common in various chemical substances. If the chlorine is present as an ion at elevated temperatures, it will corrode the construction materials mentioned above. The chlorine may have been an ion originally, liberated during heat up or in the reactor.
US 5,358,645 issued to Hong et al. disclose an apparatus and process for high temperature water oxidation, the apparatus (not in detail described) having a surface area, that may be exposed to corrosive material, composed of zirconia based ceramics. The ceramics may be employed as coatings or linings.
US 5,461,648 issued to Nauflett et al . disclose a supercritical water oxidation reactor with a corrosion-resistant lining. The inner surface of the reactor vessel is coated with artificial ceramic or diamond. A cylindrical baffle for introducing the oxygenating agent extends axially within the interior of the vessel and has its exterior surface inside the vessel coated with said artificial ceramic or diamond. US 5,552,039 issued to McBrayer, Jr. et al. disclose a turbulent flow cold-wall reactor. It mentions, inter alia, that if the atmosphere in the reaction chamber is harsh and corrosive, the inside wall of the reaction chamber should preferably be made of or covered with a coating or a liner withstanding the harsh atmosphere .
None of these US patents, is, however, discussing corrosion problems in terms of temperature dependent corrosivity, or the particular corrosion caused by the corrosive compounds discussed above.
SUMMARY OF THE INVENTION
It is consequently an object of the present invention to provide an apparatus for use in a high pressure and high temperature reaction system, specifically in a system suitable for oxidative waste treatment under supercritical water conditions, that mitigates or eliminates the occurrence of corrosion.
It is a further object of the invention to provide such an apparatus that is effective, robust, and easy to install and of low cost.
It is yet a further object of the invention to provide the apparatus in such a way that it is easily replaceable in the reaction system.
These objects among others are, according to one aspect of the invention, attained by an apparatus as claimed in Claim 1.
A further object of the present invention is to provide a method for disposing of waste using said apparatus.
Consequently, there is according to a second aspect of the present invention provided a method as claimed in Claim 22. An advantage of the present invention is that it allows the main parts of the reaction system, including the reactor itself, to be constructed of a relatively inexpensive material such as nickel based and nickel-chromium alloys, and still use or be able to treat corrosive materials in the process.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will become more fully understood from the detailed description of embodiments of the present invention given hereinbelow and the accompanying Figs. 1-3 which are given by way of illustration only, and thus are not limitative of the invention.
Fig. 1 shows a simplified block diagram of a reaction system suitable for oxidative waste treatment under supercritical water conditions wherein the present invention may be employed.
Fig. 2 shows, in cross-section, a first embodiment of an apparatus according to the present invention.
Fig. 3 shows, in cross-section, a second embodiment of an apparatus according to the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS
In the following description, for purposes of explanation and not limitation, specific details are set fourth, such as particular hardware, applications, techniques, etc. in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known methods, protocols, apparatus, and circuits are omitted so as not to obscure the description of the present invention with unnecessary details. Considering Fig. 1, the operation of a high pressure and high temperature reaction system 10 such as a system suitable for oxidative waste treatment under supercritical water conditions, will briefly be overviewed so that in the subsequent detailed description of the present invention, the operation of the inventive apparatus may be better understood.
A conventional reaction system 10 comprises a primary tank 12, a heat exchanger 14, a heater 16 and a reaction chamber 18. A primary wastewater stream 20 passes initially through the first compartment (not shown) of the heat exchanger 14, then through the heater 16, and enters the reaction chamber 18 under pressure, after it has been mixed with oxidant coming through feed line 22. The organic matter contained in the primary waste stream 20 is oxidized, and in sequence, the hot effluence passes through the second compartment (not shown) of the heat exchanger 14. As well known, heat exchangers usually have two compartments, physically isolated from each other, which, however, are heat-communicating. The second compartment transfers heat to the first compartment.
Constructing materials for the reactor and the tubing may comprise steel, nickel-based alloys, platinum, gold, titanium, zirconium, ceramics, ceramic composites and other corrosion resistant materials as the environment inside the reaction chamber and tubing may be hostile and corrosive. However, as many of the latter materials are highly expensive, an optimal compromise between cost, on one hand, and corrosion resistance, on the other hand, is to use nickel based alloys such as Hastelloy or Inconel, for the manufacturing of such equipment.
As already discussed in the prior art, there is a number of species that are very aggressive relative to these nickel based alloys within a finite temperature range, among them nitric acid, sulfuric acid and hydrochloric acid. All these three acids are strongly corrosive between about 270 and 380°C, but the corrosion rates for the latter two acids are lower by a factor of ten than the one found for nitric acid, see said Kritzer article.
It is clear from the description above of the operation of the system that the wastewater flow, as well as any additives, will be heated from initial low temperatures, which probably are close to ambient temperatures, up to supercritical temperatures (above 374°C) for the oxidative treatment of the waste, whereafter the effluent is cooled either in a heat exchanger or by mixing it with quench water or a combination of both.
The present inventors have realized that if the initial temperatures and the temperature of the cooled effluent are kept preferably well below 270°C and the temperature in the reaction chamber is kept preferably above 380°C, there is generally only two sections of a reaction system made of nickel-based alloy that may be attacked by corrosive agents such as those mentioned above contained in, or supplied to, the wastewater flow, namely a "heating" section and a "cooling" section, where the temperatures are within the temperature interval of said corrosion.
The present invention is thus concerned with such sections of the reaction system and how to design them in order to provide a reaction system of low cost and good corrosion resistance. The idea is to provide appropriate tubing (made of nickel based alloy or other, preferably relatively inexpensive, material that is not corrosive resistant) of the system with a corrosive resistant tube or liner. The number of tubes or liners, their positions and their lengths are chosen in order to protect the system from corroding.
Hereinbelow will follow a few implementation examples of the present invention. Note that the terms "corrosive" and "corrosive-resistant material" as used in the description below and in the appended claims should be understood as "corrosive" relative conventional construction material for high pressure and high temperature reaction systems suitable for supercritical water oxidation such as steel, nickel based alloys, nickel- chromium alloys and the like, at least within a given temperature interval, and "corrosive-resistant material" refers to unconventional expensive material which is corrosion- resistant relative a wide variety of harsh media such as acids, particularly the acids discussed above, halogens and the like, respectively. Examples of corrosion-resistant materials will be given below.
A first embodiment of the present invention, shown in Fig. 2, depicts an apparatus 101 for introducing nitric acid in a supercritical water flow containing ammonia or ammonium with the purpose of converting this to molecular nitrogen.
In a section of a reaction system tube 103, which preferably is the conduit between the heater 16 and the reaction chamber 18, or part of the reaction chamber itself, of Fig. 1, a separate tube or liner 105 of a corrosion resistant material is mounted, the outer surface of which is in fit with the inner surface of reaction system tube 103. Alternatively, tube 105 constitutes part of the reaction system tube 103 itself (not shown) .
A feeding pipe 107 of relatively small diameter, is mounted through an opening of tube 103 and extends substantially axially with tube 103 and liner 105, and which ends in the interior of tube 103. Preferably, feeding pipe 107 and tube 103 are concentrically arranged for transportation of fluids, the former nitric acid and the latter preheated wastewater feed, in the same directions, as indicated by arrows 109-113. The temperature of the wastewater should preferably be above 380°C, and the temperature of the nitric acid should be low, preferably considerably lower than 270°C. Note that if the concentration of the corrosive agent is low, these temperature limits are not very crucial, i.e., the corrosion would be low at temperatures slightly lower than 380°C and, particularly, at temperatures slightly higher than 270°C, e.g., 300°C.
By pumping nitric acid through the feeding pipe it will be preheated by the hot water flow and then get mixed with the supercritical water. The flow rates are such that the total flow (wastewater and nitric acid) becomes supercritical with a temperature of above 380°C after having reached a steady temperature state a certain distance 115 from the end of the feeding pipe, said distance being referred to as the heat transfer or mixing length. Accordingly, to avoid any risk of corrosion of the inner walls of tube 103, the length of the liner 105 should be of at least this length, and it should be localized to protect the inner walls of tube 103 within this length. For practical reasons, the liner 105 may have an offset 117 in the end facing the end of the feeding pipe, i.e. extend beyond (upstream of) said feeding pipe end to avoid any risk of corrosion in that region.
The material of the liner and preferably of the feeding pipe is chosen according to its corrosion resistance relative nitric acid at the occurring temperatures. Literature data shows that titanium, generally, is a suitable material, but also materials such as zirconium, platinum, tantalum, niobium and ceramics may be chosen. The entire liner, or an inner coating thereof, may be constructed of such material.
Even if a limited degree of corrosion may exist using these materials, the components are relatively cheap and easy to replace when so needed.
Preferably, there are means for positioning and/or holding the liner in place. In the embodiment showed, tube 103 is provided with an elbow at the downstream end of the mixing length to prevent liner 105 from moving further downstream. However, any suitable means for positioning and/or holding the liner, e.g. flanges at the inner walls of tube 103, may be used.
In experimental work, an injection apparatus as the one shown in Fig. 2, was used, the liner and the feeding pipe being made of titanium. The ammonia destruction was performed by pumping 65% nitric acid into the reaction system during several hours without any detected corrosion. When the liner and the feeding pipe were demounted and inspected no corrosion of these components was discovered. In contrast thereto, in an experiment in which nitric acid was pumped into a supercritical water flow containing ammonia through a T-pipe of Inconel 625, the pipe was destroyed through corrosion in just a few hours.
Consequently, by using an injection apparatus according to Fig. 2, nitric acid may safely be introduced without severe corrosion of the reaction system.
Furthermore, a substantial portion of the reaction between nitric acid and ammonia and/or ammonium will take part as early as in the section of the reaction system where the liner is localized, which further reduces the risk for severe corrosion.
Alternatively, feeding pipe 107 and tube 103 of Fig. 2 may be arranged for transportation of a wastewater feed containing a corrosive agent such as a halogen, and water or a wastewater feed in lack of such a corrosive agent, respectively. The water or wastewater in tube 103 is preferably at a supercritical temperature, whereas the corrosive wastewater may be cooler.
Referring next to Fig. 3, which illustrates an apparatus 201 according to a second embodiment of the present invention, a separate tube or liner 205 of a corrosion resistant material is mounted in a section of a reaction system tube 203, which is preferably at the effluent output or elsewhere in the exit path tubing. The outer surface of liner 205 is arranged to be in fit with the inner surface of the reaction system tube 203. A first input tube 207, is mounted through an opening of tube 203 and extends substantially axially, preferably concentrically, with tube 203 and liner 205, and which ends in the interior of tube 203. A second input tube 208 is connected to tube 203 upstream from said end of input tube 207.
Input tube 207 and input tube 208 are arranged for transporting effluent from reactor 18 containing corrosive compounds such as nitric acid, sulfur acid, or the like, and quench water, respectively, in the directions as indicated by arrows 209-213. The effluent stream is supercritical or close to supercritical, and the temperature of the quench water is low, preferably at ambient temperature.
By pumping appropriate amounts of quench water through input tube 208, the effluent input through tube 207 will be cooled effectively by the quench water and get mixed with it. The flow rates are such that the total flow (effluent and quench water) will have a temperature of below a certain temperature, e.g. 270°C, depending on concentration of corrosive compounds, after having reached a steady temperature state a certain distance 215 from the end of the input tube 207, said distance being referred to as the mixing length. Accordingly, to avoid any risk of corrosion of the inner walls of tube 203, the length of the liner 205 should be at least of this mixing length, and it should be localized to protect the inner walls of tube 203 within this length. For practical reasons, the liner 203 may have an offset 217 in the end facing the end of tube 207, i.e. extend beyond (upstream of) said tube end, to avoid any risk of corrosion in that region.
The material of the liner and preferably of tube 207, as well as suitable means for positioning and/or holding the liner in place may be chosen as in the first embodiment. The first and the second embodiments of the present invention may be modified to include a heat exchange for assisting in increasing or decreasing the temperature in tubes 103 and 203, respectively. Hereby, the lengths of liners 105 and 205, respectively, may be shortened.
As a further example of an implementation of the present invention (not illustrated in the drawings) , an effluent from the reactor containing chlorine ions is pre-cooled in a heat exchanger by part of the incoming waste stream, to a temperature well above 380°C, e.g., 400°C. The effluent is then cooled by an apparatus according to the present invention to a sufficient low temperature, e.g., 260°C, to minimize corrosion. After leaving the apparatus, the effluent water mixture is further cooled by the remaining of the waste stream.
It will be obvious that the invention may be varied in a plurality of ways. For instance, the geometry and function of the reaction system and the appearance of the tubing may deviate substantially from the description above. Such and other variations are not to be regarded as a departure from the scope of the invention. All such modifications as would be obvious to one skilled in the art are intended to be included within the scope of the appended claims.

Claims

1. In a high pressure and high temperature reaction system suitable for oxidative waste treatment, particularly a reaction system for supercritical water oxidation (SCWO) , a method for injecting a first fluid of a first temperature at a first flow rate into a second fluid of a second temperature at a second flow rate, said first fluid being corrosive only in a temperature range which excludes said second temperature and includes said first temperature or which lies between said first and second temperatures, characterized by
transporting the first fluid in a first conduit (107, 207) adapted therefore;
- transporting the second fluid in a second conduit (103, 203) adapted therefore, wherein said first conduit (107, 207) ends in the interior of said second conduit (103, 203) , and thus communicates with said second conduit; and
- mixing the first and the second fluids (115, 215) in said second conduit within a mixing length downstream of said first conduit end, wherein said second conduit is provided with a tube or liner (105, 205) having at least its inner surface area made of a corrosion resistant material, and extending along said mixing length (115, 215) to protect said second conduit (103, 203) from corroding; wherein
- the first and second temperatures and the first and second flow rates are selected such that a temperature of the mixed fluids downstream of said mixing length (115, 215) is obtained, at which said first fluid being substantially non-corrosive.
2. The method as claimed in Claim 1, wherein said first fluid is corrosive at said selected first temperature and wherein at least the inner surface area of said first conduit (107, 207) is made of a corrosion resistant material to protect said first conduit (107, 207) from corroding.
3. The method as claimed in Claim 1 or 2, wherein said first fluid contains nitric acid and said corrosive temperature range at which said first fluid is corrosive ranges between about 270°C and 380°C
4. The method as claimed in any of Claims 1-3, wherein said first fluid contains sulfuric acid and/or hydrochloric acid and/or any halogen.
5. The method as claimed in any of Claims 1-4, wherein said second temperature is selected to be higher than said temperature range at which said first fluid is corrosive, and wherein the first and second temperatures and the first and second flow rates are selected such that said temperature of the mixed fluids downstream of said mixing length is higher than said temperature range at which said first fluid is corrosive.
6. The method as claimed in Claim 5, wherein said second fluid contains supercritical wastewater.
7. The method as claimed in Claim 6, wherein said second fluid contains nitrogenous compound.
8. The method as claimed in any of Claims 3-7, comprising feeding the mixed fluids in said second conduit (103, 203) to a reactor (18) of the high pressure and high temperature reaction system (10) for oxidation of waste material.
9. The method as claimed in any of Claims 3-7, wherein said second conduit (103, 203) is part of a reactor (18) of the high pressure and high temperature reaction system, wherein waste material is oxidized.
10. The method as claimed in any of Claims 1-4, wherein said second temperature is selected to be lower than said temperature range at which said first fluid is corrosive, and wherein the first and second temperatures and the first and second flow rates are selected such that said temperature of the mixed fluids downstream of said mixing length is lower than said temperature range at which said first fluid is corrosive.
11. The method as claimed in Claim 10, wherein said second fluid contains cooling water.
12. The method as claimed in Claim 11, wherein said first fluid contains destructed supercritical wastewater output from a reactor (18) of the high pressure and high temperature reaction system (10) .
13. The method as claimed in Claim 12, wherein the mixed fluids in said second conduit (103, 203) are output from the high pressure and high temperature reaction system (10) .
14. The method as claimed in any of Claims 1-13, wherein said at least inner surface area of the tube or liner (105, 205) is made of a material selected from the group of titanium, zirconium, platinum, tantalum, niobium and alloys thereof.
15. A high pressure and high temperature reaction system suitable for oxidative waste treatment, particularly a reaction system for supercritical water oxidation (SCWO) , characterized in
- a first conduit (107, 207) adapted to transport a first fluid of a first temperature at a first flow rate;
- a second conduit (103, 203) adapted to transport a second fluid of a second temperature at a second flow rate, said first fluid being corrosive in a temperature range which excludes said second temperature and includes said first temperature or which lies between said first and second temperatures; wherein - said first conduit (107, 207) ends in the interior of said second conduit (103, 203) , and thus communicates with said second conduit, such that the first and the second fluids can be mixed in said second conduit (103, 203) within a mixing length (115, 215) downstream of said first conduit end in such manner that a temperature of the mixed fluids downstream of said mixing length (115, 215) is obtained, at which said first fluid is substantially non-corrosive; and
- a tube or liner (105, 205) with at least its inner surface area made of a corrosion resistant material, said tube or liner being located in, or constituting part of, said second conduit and extending along said mixing length (115, 215) to protect said second conduit from corroding.
16. The reaction system as claimed in Claim 15, wherein said first conduit is adapted to transport a first fluid, which is corrosive at said selected first temperature, and wherein at least the inner surface area of said first conduit (107, 207) is made of a corrosion resistant material to protect said first conduit (107, 207) from corroding.
17. The reaction system as claimed in Claim 15 or 16, wherein said first fluid contains nitric acid and said corrosive temperature range at which said first fluid is corrosive ranges between about 270°C and 380°C
18. The reaction system as claimed in any of Claims 15-17, wherein said first fluid contains sulfuric acid and/or hydrochloric acid and/or any halogen.
19. The reaction system as claimed in any of Claims 15-18, wherein said second conduit is adapted to transport a second fluid at a second temperature, which is higher than said temperature range at which said first fluid is corrosive, and to transport the mixed fluids, said mixed fluids being of a temperature downstream of said mixing length, which is also higher than said temperature range at which said first fluid is corrosive.
20. The reaction system as claimed in Claim 19, wherein said second fluid contains supercritical wastewater.
21. The reaction system as claimed in Claim 20, wherein said second fluid contains nitrogenous compound.
22. The reaction system as claimed in any of Claims 17-21, further comprising a reactor (18) for oxidation of waste material, wherein said second conduit is adapted to feeding the mixed fluids to said reactor.
23. The reaction system as claimed in any of Claims 17-21, comprising a reactor (18) for oxidation of waste material, wherein said second conduit (103, 203) is part of said reactor.
24. The reaction system as claimed in any of Claims 15-18, wherein said second conduit is adapted to transport a second fluid at a second temperature, which is lower than said temperature range at which said first fluid is corrosive, and wherein said second conduit is adapted to transport the mixed fluids, said mixed fluids being of a temperature downstream of said mixing length, which is lower than said temperature range at which said first fluid is corrosive.
25. The reaction system as claimed in Claim 24, wherein said second fluid contains cooling water.
26. The reaction system as claimed in Claim 25, comprising a reactor (18), wherein said first conduit is adapted to transport a first fluid, which contains destructed supercritical or subcritical wastewater output from said reactor.
27. The reaction system as claimed in Claim 13, comprising a high pressure and high temperature reaction system output, wherein said second conduit is adapted to transport said mixed fluids to said system output.
28. The reaction system as claimed in any of Claims 15-27, wherein said at least inner surface area of the tube or liner (105, 205) is made of a material selected from the group of titanium, zirconium, platinum, tantalum, niobium and alloys thereof.
29. The reaction system as claimed in any of Claims 15-28, wherein the tube or liner (105, 205) is removably arranged in said second conduit.
30. The reaction system as claimed in any of Claims 15-29, wherein said tube or liner (105, 205) is extending a predetermined distance (117, 217) upstream of said first conduit end.
31. The reaction system as claimed in any of Claims 15-30, wherein said second conduit is provided with means for holding and/or positioning the tube or liner (105, 205) in said second conduit (103, 203) .
32. The reaction system as claimed in Claim 31, wherein said second conduit (103, 203) is provided with an elbow (119, 219) at the downstream end of the mixing length (115, 215) in order to prevent said tube or liner (105, 205) from moving along the inner surface of said second conduit (103, 203) in the downstream direction.
EP00959090A 1999-09-03 2000-08-31 A high pressure and high temperature reaction system Expired - Lifetime EP1224151B1 (en)

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SE9903113A SE518803C2 (en) 1999-09-03 1999-09-03 Method and reaction system with high pressure and high temperature suitable for supercritical water oxidation
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Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6475396B1 (en) 2000-11-14 2002-11-05 Hydroprocessing, Llc Apparatus and method for applying an oxidant in a hydrothermal oxidation process
FR2871794B1 (en) * 2004-06-18 2007-07-20 Centre Nat Rech Scient Cnrse PROCESS FOR TREATING AQUEOUS EFFLUENTS COMPRISING METALLIC SALTS OF NITRATE OR NITRITE TYPE
ITMI20041240A1 (en) * 2004-06-21 2004-09-21 3V Green Eagle S P A PARTICULAR COATING FOR EQUIPMENT TO REALIZE OXIDATIVE PROCESSES AND EQUIPMENT INCLUDING SUCH COATING
FR2874513B1 (en) * 2004-08-25 2006-11-03 Commissariat Energie Atomique DIPOSITIVE AND PLANT FOR INJECTING PARTICULATE MATERIALS IN AN ENCLOSURE AND ASSOCIATED METHOD.
AU2004322947B2 (en) 2004-09-01 2010-05-13 Hatch Ltd. Composite sparger
US7976774B2 (en) 2004-09-01 2011-07-12 Hatch Ltd. Composite sparger
SE529428C2 (en) * 2006-05-02 2007-08-07 Sandvik Intellectual Property Austenitic stainless steel alloy component, e.g. tube, for use in supercritical water oxidation plants comprises predetermined amounts of chromium and nickel
IL173547A0 (en) * 2006-02-06 2006-07-05 Pyernik Rutman Supercritical oxidation process for the treatment of corrosive materials
US7998418B1 (en) 2006-06-01 2011-08-16 Nanotek, Llc Evaporator and concentrator in reactor and loading system
US7641860B2 (en) * 2006-06-01 2010-01-05 Nanotek, Llc Modular and reconfigurable multi-stage microreactor cartridge apparatus
US7854902B2 (en) * 2006-08-23 2010-12-21 Nanotek, Llc Modular and reconfigurable multi-stage high temperature microreactor cartridge apparatus and system for using same
US7615385B2 (en) 2006-09-20 2009-11-10 Hypres, Inc Double-masking technique for increasing fabrication yield in superconducting electronics
WO2008118808A1 (en) 2007-03-23 2008-10-02 Advion Bioscience, Inc. Liquid chromatography-mass spectrometry
JP2012522635A (en) * 2009-04-01 2012-09-27 アース・リニューアル・グループ，エルエルシー Improved aqueous phase oxidation process
US9272936B2 (en) 2009-04-01 2016-03-01 Earth Renewal Group, Llc Waste treatment process
US8481800B2 (en) * 2009-04-01 2013-07-09 Earth Renewal Group, Llc Aqueous phase oxidation process
US7915474B2 (en) * 2009-04-01 2011-03-29 Earth Renewal Group, Llc Aqueous phase oxidation process
US8168847B2 (en) * 2009-04-01 2012-05-01 Earth Renewal Group, Llc Aqueous phase oxidation process
US7951988B2 (en) * 2009-04-01 2011-05-31 Earth Renewal Group, Llc Aqueous phase oxidation process
US8115047B2 (en) * 2009-04-01 2012-02-14 Earth Renewal Group, Llc Aqueous phase oxidation process
JP5563663B2 (en) * 2009-10-20 2014-07-30 アンガス ケミカル カンパニー Isothermal reactor for hydrocarbon nitration
JP5630152B2 (en) * 2010-08-31 2014-11-26 株式会社リコー Waste liquid treatment equipment
CN105163841A (en) * 2013-05-02 2015-12-16 英派尔科技开发有限公司 System and method for reducing corrosion in a reactor system using corrosion protection layers
WO2015016931A1 (en) * 2013-08-01 2015-02-05 Empire Technology Development Llc Corrosion-resisant surfaces for reactors
US10221488B2 (en) * 2015-09-18 2019-03-05 General Electric Company Supercritical water method for treating internal passages
KR20170050076A (en) * 2015-10-29 2017-05-11 주식회사 엘지화학 Mixer and reactor comprising the same
CN105731626A (en) * 2016-02-29 2016-07-06 东莞道汇环保科技有限公司 Wastewater treatment system
WO2020264530A1 (en) 2019-06-28 2020-12-30 Battelle Memorial Institute Destruction of pfas via an oxidation process and apparatus suitable for transportation to contaminated sites
CN111762867B (en) * 2020-07-14 2021-10-08 西安交通大学 Supercritical water oxidation evaporation wall type reactor
WO2023196883A1 (en) * 2022-04-05 2023-10-12 Revive Environmental Technology, Llc Preventing hydrogen embrittlement during supercritical water oxidation (scwo) of pfas

Family Cites Families (113)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2735265A (en) 1956-02-21 Bois eastman
US1725782A (en) 1925-09-17 1929-08-27 Florez Luis De Method and apparatus for flow control
US1988456A (en) 1930-03-24 1935-01-22 Milo Ab Gas turbine system
US1986196A (en) 1933-05-04 1935-01-01 Universal Oil Prod Co Apparatus for conducting reactions at elevated pressures
US2545384A (en) 1944-08-05 1951-03-13 Phillips Petroleum Co Insulation of catalyst chambers
US2398546A (en) 1944-11-06 1946-04-16 Phillips Petroleum Co Thermal insulation of vessels
US2476598A (en) 1945-02-16 1949-07-19 Hall Lab Inc Treatment of steam boiler water
US2519616A (en) 1946-06-15 1950-08-22 Universal Oil Prod Co Heating apparatus
US2647368A (en) 1949-05-09 1953-08-04 Hermann Oestrich Method and apparatus for internally cooling gas turbine blades with air, fuel, and water
US2665249A (en) 1950-03-27 1954-01-05 Sterling Drug Inc Waste disposal
US2697910A (en) 1950-07-29 1954-12-28 Thermal Res And Engineering Co Fluid fuel burner with self-contained fuel vaporizing unit
US2692800A (en) 1951-10-08 1954-10-26 Gen Electric Nozzle flow control
US2767233A (en) 1952-01-07 1956-10-16 Chemical Construction Corp Thermal transformation of hydrocarbons
FR1026068A (en) 1953-12-14 1953-04-23 Sterling Drug Inc Process and installation for the destruction by oxidation of organic matter contained in black water such as waste sulphite liquors and for the production of thermal energy
NL90468C (en) 1955-02-09 1900-01-01
US3047371A (en) 1955-05-13 1962-07-31 Hoechst Ag Device for carrying out chemical reactions at high temperatures
US3047003A (en) 1960-04-18 1962-07-31 Gamewell Co Flow proportioning system for foam producing apparatus
US3129587A (en) 1960-10-11 1964-04-21 Honeywell Regulator Co Flow sensing device
US3101592A (en) 1961-01-16 1963-08-27 Thompson Ramo Wooldridge Inc Closed power generating system
US3149176A (en) 1961-07-13 1964-09-15 Gulf Research Development Co Hydrodealkylation process
US3207572A (en) 1961-09-12 1965-09-21 Ass Pulp & Paper Mills Wet combustion of waste liquors
US3282459A (en) 1964-10-02 1966-11-01 Allis Chalmers Mfg Co Pressure vessel having concentric casings
US3449247A (en) 1965-10-23 1969-06-10 William J Bauer Process for wet oxidation of combustible waste materials
US3464885A (en) 1966-04-05 1969-09-02 Halliburton Co Methods for effecting continuous subterranean reactions
US3414004A (en) 1966-05-16 1968-12-03 Pan American Petroleum Corp Film injector
US3472632A (en) 1966-11-25 1969-10-14 Universal Oil Prod Co Internally lined reactor for high temperatures and pressures and leakage monitoring means therefor
US3431075A (en) 1966-12-23 1969-03-04 Phillips Petroleum Co Production of carbon black
US3515520A (en) 1967-02-13 1970-06-02 Universal Oil Prod Co Reactor with internal protective sleeve for corrosive systems
US3606999A (en) 1967-08-04 1971-09-21 Harold L Lawless Method of and apparatus for carrying out a chemical or physical process
US3549314A (en) 1968-05-20 1970-12-22 Chemical Construction Corp Oxidation of black liquor
US3853759A (en) 1968-06-06 1974-12-10 J Titmas Dynamic hydraulic column activation method
US3626874A (en) 1968-10-22 1971-12-14 Action Concepts Technology Inc System for collecting and disposing of ordinary refuse by converting it into useful energy, without pollution
US3743606A (en) 1970-01-23 1973-07-03 Texaco Development Corp Synthesis gas generation
US3654070A (en) 1970-04-02 1972-04-04 Sterling Drug Inc Oxidation and reuse of effluent from oxygen pulping of raw cellulose
AU428247B2 (en) 1970-05-08 1972-09-13 Wet combustion of waste liquor
US3674045A (en) 1970-07-14 1972-07-04 Bendix Corp Vortex valve fluid oscillator
US3849536A (en) 1970-08-31 1974-11-19 Ass Pulp & Paper Mills Wet combustion of waste liquors
US3716474A (en) 1970-10-22 1973-02-13 Texaco Inc High pressure thermal treatment of waste oil-containing sludges
US3816338A (en) 1971-02-08 1974-06-11 Cpc International Inc Process for the reactivation of powdered carbon
US3682142A (en) 1971-05-06 1972-08-08 Intern Materials Method and means for generating hydrogen and a motive source incorporating same
US3899923A (en) 1971-05-13 1975-08-19 Teller Environmental Systems Test process and apparatus for treatment of jet engine exhaust
US4075281A (en) 1971-05-24 1978-02-21 Allied Chemical Corporation Purification of carbonate process solutions
US3761409A (en) 1971-10-06 1973-09-25 Texaco Inc Continuous process for the air oxidation of sour water
US3876497A (en) 1971-11-23 1975-04-08 Sterling Drug Inc Paper mill waste sludge oxidation and product recovery
US3849075A (en) 1972-05-08 1974-11-19 Union Carbide Corp Cracking reactor
US3804756A (en) 1972-06-22 1974-04-16 Standard Oil Co Environmentally safe disposal of organic pollutants
JPS5226343B2 (en) 1972-09-08 1977-07-13
DE2247841C3 (en) 1972-09-29 1981-02-12 Michigan Tech Fund, Houghton, Mich. (V.St.A.) Process for the wet oxidation of carbonaceous waste material
US3984311A (en) 1972-10-05 1976-10-05 The Dow Chemical Company Wet combustion of organics
US3852192A (en) 1973-03-29 1974-12-03 Barber Colman Co Reactor for wet oxidation of organic matter
US3876536A (en) 1973-04-24 1975-04-08 Sterling Drug Inc Waste oxidation process
US3886972A (en) 1973-12-06 1975-06-03 Shell Oil Co Core flow nozzle
US3912626A (en) 1974-03-18 1975-10-14 Sterling Drug Inc Catalyzed process and catalyst recovery
US3945805A (en) 1974-04-18 1976-03-23 Modine Manufacturing Company Reactor-generator apparatus
US3945806A (en) 1974-04-18 1976-03-23 Modine Manufacturing Company Reactor-generator
JPS5347235B2 (en) 1974-05-15 1978-12-19
US4174280A (en) 1974-07-17 1979-11-13 Sterling Drug Inc. Oxidation process
US3929429A (en) 1974-09-26 1975-12-30 Texaco Inc Fuel gas from solid carbonaceous fuels
US4124528A (en) 1974-10-04 1978-11-07 Arthur D. Little, Inc. Process for regenerating adsorbents with supercritical fluids
US3900300A (en) 1974-10-19 1975-08-19 Universal Oil Prod Co Vapor-liquid separation apparatus
US3978661A (en) 1974-12-19 1976-09-07 International Power Technology Parallel-compound dual-fluid heat engine
US4013560A (en) 1975-04-21 1977-03-22 Sterling Drug Inc. Energy production of wet oxidation systems
US4010098A (en) 1975-05-29 1977-03-01 Barber-Colman Company Resource recovery from disposal of solid waste and sewage sludge
US4100730A (en) 1975-06-04 1978-07-18 Sterling Drug, Inc. Regulation of a wet air oxidation unit for production of useful energy
FR2314426A1 (en) * 1975-06-10 1977-01-07 Atomac Kunststoff Dieter Schmi Connecting pipe assembly for internally enamel lined reactor - made of outer carrying sleeve with removable corrosion resistant liner
US4113446A (en) 1975-07-22 1978-09-12 Massachusetts Institute Of Technology Gasification process
US4000068A (en) 1975-08-12 1976-12-28 Phillips Petroleum Company Polluted water purification
US4199545A (en) 1975-08-20 1980-04-22 Thagard Technology Company Fluid-wall reactor for high temperature chemical reaction processes
US4005803A (en) 1975-08-22 1977-02-01 Deere & Company Chemical concentrate injection system
US3977966A (en) 1975-09-24 1976-08-31 Sterling Drug Inc. Purification of non-biodegradable industrial wastewaters
US4017421A (en) 1975-12-16 1977-04-12 Othmer Donald F Wet combustion process
DE2609846C2 (en) 1976-03-10 1982-05-19 Sachs Systemtechnik Gmbh, 8720 Schweinfurt Drinking water purification device
JPS5816934B2 (en) 1976-03-31 1983-04-04 日揮株式会社 Activated carbon regeneration equipment
US4147624A (en) 1976-04-15 1979-04-03 Arthur D. Little, Inc. Wastewater treatment with desorbing of an adsorbate from an adsorbent with a solvent in the near critical state
US4146359A (en) 1976-06-25 1979-03-27 Occidental Petroleum Corporation Method for reacting nongaseous material with a gaseous reactant
DE2640603B2 (en) 1976-09-09 1978-10-19 Bayer Ag, 5090 Leverkusen Process for the wet oxidation of organic substances
DE2657011B2 (en) 1976-12-16 1978-12-14 Hoechst Ag, 6000 Frankfurt Process for cleaning the waste water resulting from the production of hydroxyaromatics with the simultaneous recovery of alkali sulphate
US4094815A (en) 1977-06-02 1978-06-13 Aluminum Company Of America Regeneration of activated carbon having materials adsorbed thereon
US4217218A (en) 1977-12-27 1980-08-12 Sterling Durg Inc. Removal of solids from a wet oxidation reactor
JPS54110199A (en) 1978-02-17 1979-08-29 Sumitomo Aluminium Smelting Co Method of removing organics from circulating aluminic acid alkali solution
US4272383A (en) 1978-03-17 1981-06-09 Mcgrew Jay Lininger Method and apparatus for effecting subsurface, controlled, accelerated chemical reactions
CH635049A5 (en) 1978-05-23 1983-03-15 Bbc Brown Boveri & Cie METHOD AND DEVICE FOR REGENERATING ACTIVE CARBON.
US4191012A (en) 1978-07-10 1980-03-04 Stoddard Xerxes T Wet oxidation engine
US4326957A (en) 1978-07-21 1982-04-27 Pall Corporation Vented filter spigot for intravenous liquid administration apparatus
US4229296A (en) 1978-08-03 1980-10-21 Whirlpool Corporation Wet oxidation system employing phase separating reactor
US4221763A (en) 1978-08-29 1980-09-09 Cities Service Company Multi tube high pressure, high temperature reactor
FR2434649A1 (en) 1978-09-01 1980-03-28 Ugine Kuhlmann REACTOR MADE FROM STEEL PARTICULARLY RESISTANT TO THE EFFECTS OF OXO SYNTHESIS
US4241722A (en) 1978-10-02 1980-12-30 Dickinson Norman L Pollutant-free low temperature combustion process having carbonaceous fuel suspended in alkaline aqueous solution
US4380960A (en) 1978-10-05 1983-04-26 Dickinson Norman L Pollution-free low temperature slurry combustion process utilizing the super-critical state
US4292953A (en) 1978-10-05 1981-10-06 Dickinson Norman L Pollutant-free low temperature slurry combustion process utilizing the super-critical state
US4212735A (en) 1979-03-01 1980-07-15 Hydroscience, Inc. Destruction method for the wet combustion of organics
US4384897A (en) 1981-11-23 1983-05-24 The Regents Of The University Of California Method of treating biomass material
US4284015A (en) 1979-03-26 1981-08-18 Dickinson Norman L Pollution-free coal combustion process
US4221577A (en) 1979-04-03 1980-09-09 Combustion Engineering, Inc. Gas-liquid separator
US4338199A (en) 1980-05-08 1982-07-06 Modar, Inc. Processing methods for the oxidation of organics in supercritical water
US4377066A (en) 1980-05-27 1983-03-22 Dickinson Norman L Pollution-free pressurized fluidized bed combustion utilizing a high concentration of water vapor
US4344785A (en) 1980-10-02 1982-08-17 Ppg Industries, Inc. Modular molten glass column
US4384959A (en) 1980-12-29 1983-05-24 Sterling Drug Inc. Wet oxidation process utilizing dilution of oxygen
US4370223A (en) 1980-12-31 1983-01-25 Chevron Research Company Coking hydrocarbonaceous oils with an aqueous liquid
US4378976A (en) 1981-08-14 1983-04-05 Institute Of Gas Technology Combined sonic agglomerator/cross flow filtration apparatus and process for solid particle and/or liquid droplet removal from gas streams
US4869833A (en) * 1986-04-03 1989-09-26 Vertech Treatment Systems, Inc. Method and apparatus for controlled chemical reactions
JP3307391B2 (en) * 1991-04-09 2002-07-24 モダー，インコーポレイテッド Method of oxidizing combustible corrosive substances in high temperature water oxidation environment in high temperature water oxidation equipment
JP3274280B2 (en) * 1994-03-30 2002-04-15 株式会社神戸製鋼所 High pressure reaction vessel equipment
TW259720B (en) * 1994-06-29 1995-10-11 Kimberly Clark Co Reactor for high temperature, elevated pressure, corrosive reactions
US5552039A (en) * 1994-07-13 1996-09-03 Rpc Waste Management Services, Inc. Turbulent flow cold-wall reactor
US5461648A (en) * 1994-10-27 1995-10-24 The United States Of America As Represented By The Secretary Of The Navy Supercritical water oxidation reactor with a corrosion-resistant lining
US5545337A (en) * 1994-11-29 1996-08-13 Modar, Inc. Ceramic coating system or water oxidation environments
US5674405A (en) * 1995-07-28 1997-10-07 Modar, Inc. Method for hydrothermal oxidation
US5804066A (en) * 1996-02-08 1998-09-08 Aerojet-General Corporation Injector for SCWO reactor
JP3297680B2 (en) * 1997-04-23 2002-07-02 株式会社荏原製作所 Supercritical reactor and method
JPH11239722A (en) * 1997-12-18 1999-09-07 General Atomics Inc Pressure reactor
FR2780986B1 (en) * 1998-07-10 2000-09-29 Electrolyse L PROCESS FOR TRANSFORMATION OF CHEMICAL STRUCTURES IN A FLUID UNDER PRESSURE AND AT TEMPERATURE AND DEVICE FOR ITS IMPLEMENTATION
JP3660819B2 (en) * 1998-12-25 2005-06-15 オルガノ株式会社 Cooling device for supercritical processing fluid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0117915A1 *

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DE60014943D1 (en) 2004-11-18
ES2231249T3 (en) 2005-05-16
AU7047300A (en) 2001-04-10
WO2001017915A1 (en) 2001-03-15
EP1224151B1 (en) 2004-10-13
SE9903113L (en) 2001-03-04
SE9903113D0 (en) 1999-09-03
SE518803C2 (en) 2002-11-26
JP4752074B2 (en) 2011-08-17
JP2003508222A (en) 2003-03-04
DE60014943T2 (en) 2005-03-10
ATE279377T1 (en) 2004-10-15
US6958122B1 (en) 2005-10-25

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